Reactive intermediates carbenes

Photolysis of ketene with light of wavelength 300-370 m/x produces the reactive intermediate carbene, which is capable of a variety of insertion and addition reactions. 

The formation of reactive intermediates provides possible opportunities for new reaction design. An attractive highly reactive intermediate, carbenes, which demonstrate numerous useful synthetic pathways, most notably by addition to alkenes and alkynes and also insertion into X-H bonds, where X is both carbon and heteroatoms, suffers from problems associated with their accessibility. Undoubtedly, the most useful class of precursor is the diazo compounds, whose safety problems restrict their use. For the specific case of vinylidenes, an attractive possibility is a terminal alkyne which is isomeric with a vinylidene. Although the thermolysis appears to effect this transformation (Equation 1.1, path a), the extraordinarily high temperatures required make the prospect of a transition metal-catalyzed version (Equation 1.1, path b) attractive. The early studies of Werner [6] using Rh and Bruce and co-workers [7] using Ru proved the facility with which such species would form however, the studies focused on the formation and isolation of the vinylidene-metal complexes and their stoichiometric reactions. 

Chiefly in an hydrophobic medium, a base can extract the proton on position 2 leading to a reactive intermediate (able to give subsequent condensation) that could be an ylid (35, 36) or a carbene (37), though no dimer has ever been isolated as is the case with benzothiazolium (32, 38). Two mechanisms have been proposed for explaining the particular reactivity of thiazolium ... 

Dipoles without a double bond but with internal octet stabilization, referred to as the allyl anion type, are shown in Table 3. A third group, 1,3-dipoles without octet stabilization such as vinyl carbenes, iminonitrenes, etc., is known, but these are all highly reactive intermediates with only transient existence. Reference is made to this type where appropriate and in Table 4 (p. 146). 

Casey CP (1981) Metal-carbene complexes. In Jones M Jr, Moss RA (eds) Reactive intermediates. Wiley, New York, p 135... 

Both rhodium and osmium porphyrins are active for the cyclopropanation of alkenes. The higher activity of the rhodium porphyrin catalysts can possibly be attributed to a more reactive, cationic carbene intermediate, which so far has defied isolation. The neutral osmium carbene complexes are less active as catalysts but the mono- and bis-carbene complexes can be isolated as a result. 

The main danger factor is the polyhaiogenation on one carbon site only. The substitution (1) or elimination (2) reaction can then lead to an intermediate carbene (or to a transition state that has this character). Its reactivity and instability will create accidents. 

As demonstrated in the two previous sections, TRIR spectroscopy can be used to provide direct structural information concerning organic reactive intermediates in solution as well as kinetic insight into mechanisms of prodnct formation. TRIR spectroscopy can also be used to examine solvent effects by revealing the inflnence of solvent on IR band positions and intensities. For example, TRIR spectroscopy has been used to examine the solvent dependence of some carbonylcarbene singlet-triplet energy gaps. Here, we will focns on TRIR stndies of specific solvation of carbenes. 

In this chapter, we will consider examples of RIs characterized by a hypervalent or valency-deficient carbon, such as carbocations, carbenes, carbanions, and carbon radicals. In the first part, we will consider examples that take advantage of stabilization and persistence to determine their structures by single crystal X-ray diffraction. In the second part we will describe several examples of transient reactive intermediates in crystals. ... 

The textbook definition of a reactive intermediate is a short-lived, high-energy, highly reactive molecule that determines the outcome of a chemical reaction. Well-known examples are radicals and carbenes such species cannot be isolated in general, but are usually postulated as part of a reaction mechanism, and evidence for their existence is usually indirect. In thermal reactivity, for example, the Wheland intermediate (Scheme 9.1) is a key intermediate in aromatic substitution. 

Reactions Involving Carbocations, Carbenes, and Radicals as Reactive Intermediates... 

---